CN109817891B - Method for preparing nano structure on surface of titanium material in situ - Google Patents
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Abstract
The invention relates to the field of lithium ion battery cathode materials, in particular to a method for preparing a nano structure on the surface of a titanium material in situ. The method comprises the following steps: 1) preparing fluorine-containing electrolyte, and electrolyzing by taking a titanium substrate as an anode and graphite as a cathode to obtain a titanium substrate; 2) corroding a titanium oxide layer on the surface of the titanium substrate, then placing the titanium oxide layer in alkali liquor for hydrothermal treatment, and after hydrothermal treatment, carrying out acid liquor impregnation and annealing treatment to obtain a pre-matrix; 3) etching the surface of the pre-matrix by utilizing gas phase etching, and soaking the pre-matrix in tetrabutyl titanate after etching to obtain a precursor; 4) and putting the precursor into concentrated hydrochloric acid for hydrothermal treatment to obtain the titanium material with the surface in-situ grown complex titanium oxide nano structure. According to the invention, the villiform titanium oxide structure is further prepared on the basis of the titanium oxide nanowire array through further soaking and hydrothermal modes, so that the lithium ions are more conveniently and stably inserted and removed.
Description
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to a method for preparing a nano structure on the surface of a titanium material in situ.
Background
With the rapid development of micro-electro-mechanical systems (MEMS) and electric vehicles, the requirements for further improving the energy density, power density, cycle performance, etc. of lithium ion batteries are more and more urgent, and the development of novel positive and negative electrode materials is the key to improving the battery performance. The nano-electrode is one of the leading issues in the field of lithium ion battery research at present, and numerous researches show that the nano-electrode has many unique physical and chemical properties, such as large specific surface area, short ion migration stroke, small electrode polarization degree, high reversible capacity, long cycle life and the like, and related research results are reported in journal of Science and the like (Nature,2001,414(6861): 359-367; Science,2010,330: 1515-1520; Nature Communications,2013,4:1331) for many times in recent years.
TiO2(B) Is TiO2Metastable phase of (2), also known as TiO2Of (A) is a "fourth state" or monoclinic TiO2And (4) crystals. TiO 22(B) Not only having Li4Ti5O12Similar advantages, such as low cost, low toxicity, safety, and larger capacity, the theoretical specific capacity reaches 335mAh/g (Li)4Ti5O12175mAh/g only), 372mAh/g close to graphite electrode, and is expected to replace Li4Ti5O12Graphite, etc., are considered to be very promising negative electrode materials for lithium ion batteries.
Hitherto, with respect to TiO2(B) The preparation of the three-dimensional electrode material, the related research of the performance and the like are rarely reported. Generally, TiO2(B) Is a proton titanate (H) of a layered or tunnel structure2TinO2n+1) Formed by dehydration, by hydrothermal reaction, solid-phase reaction, sol-gel method, etc., to obtain TiO2(B) The morphology may be nanotubes, nanosheets, nanoribbons, or the like. The hydrothermal method has the advantages of low production cost, controllable process, good product dispersibility, high purity and the like, and is widely applied to the field of nano material preparation. Hydrothermal synthesis of TiO2(B) First, amorphous or anatase TiO2Placing the nano powder in a high-temperature hydrothermal kettle, carrying out chemical reaction with concentrated alkali liquor for a certain time, and then carrying out ion exchange, roasting and the likeObtaining TiO2(B) Nanomaterials (Chemistry of materials, 2009,21(20): 4778-4783; foreign patent: US 10021263). The high orientation nano array can be prepared by a hydrothermal method, and the process generally needs to prefabricate nano particles or thin films on a substrate as the seeds for the oriented growth of nano rods or wires (the university of Beijing science and technology, 2010,32(4): 487-493; Chinese patent: CN 106316151A).
However, the titanium oxide nano structure prepared by the method has limited specific surface area and further improved space.
Disclosure of Invention
In order to solve the problem that the specific surface area of a titanium oxide nano-structure array prepared on the surface of a titanium material is limited in the prior art, the invention provides a method for preparing a nano-structure on the surface of the titanium material in situ. It is to achieve the following several purposes: firstly, the specific surface area of the surface nano structure of the existing titanium material is further improved; secondly, the electrochemical performance of the titanium material is further improved through the preparation of the nano structure.
In order to achieve the purpose, the invention adopts the following technical scheme.
A method for preparing a nano structure on the surface of a titanium material in situ, which comprises the following steps:
1) preparing fluorine-containing electrolyte, taking the pretreated titanium substrate as an anode and graphite as a cathode for electrolysis, and cleaning to obtain the titanium substrate with a titanium oxide layer;
2) corroding a titanium oxide layer on the surface of the titanium substrate in a corrosion liquid soaking mode, then placing the titanium substrate in alkali liquor for hydrothermal treatment, soaking in acid liquor after hydrothermal treatment, and annealing to obtain a pre-matrix;
3) etching the surface of the pre-matrix by using a gas phase etching method, and then placing the pre-matrix in tetrabutyl titanate for low-pressure dipping to obtain a precursor;
4) and putting the precursor into concentrated hydrochloric acid for hydrothermal treatment, and obtaining the titanium material with the surface in-situ grown complex titanium oxide nanostructure after hydrothermal treatment.
The pretreatment of the titanium substrate comprises the processes of oil removal, preliminary anodic oxidation film formation, oxide film removal and the like, and preparation is made for the subsequent preparation of the titanium oxide nanowire array. Preparing a high-orientation titanium oxide nanowire array on the surface of a titanium substrate by adopting a conventional TNTA preparation method, and then treating the nanowire array in a vapor etching mode to greatly reduce the surface evenness of the nanowire array so as to further grow a titanium nanostructure in the subsequent growth. In the subsequent process, tetrabutyl titanate is fully impregnated into the nano array on the surface of the titanium substrate in a low-pressure impregnation mode, in the subsequent hydrothermal process, a grass-like structure can further grow in the dents etched by the gas phase on the basis of the original nano array, the specific surface area of the titanium cathode material is further increased, the orderliness and the integrity of the original nano array are maintained, the original advantages are kept, and the electrochemical performance is further optimized on the basis.
Preferably, the fluorine-containing electrolyte in the step 1) is an ethylene glycol solution with a fluoride concentration of 0.1-1.0 wt%.
The electrolyte with the proportion can generate a highly uniform and smooth titanium oxide layer on the surface of the titanium substrate in the electrolytic process.
Preferably, in the electrolysis process in the step 1), the direct current voltage is 25-70V, the electrolysis time is 10-180 min, and the distance between the two electrodes is 1.5-2.5 cm.
The thickness of the titanium oxide layer under the electrolysis condition is moderate, the thickness of the titanium oxide layer can be adjusted through electrolysis time, and the cut surface is uniform and flat, so that the uniformity of the titanium oxide nanowire array on the surface of the precursor obtained through subsequent preparation is higher.
Preferably, the etching solution in the step 2) consists of water, 40-45 wt% of hydrogen fluoride and chromium trioxide, and the water and the hydrogen fluoride are firstly mixed in a ratio of 100: (7-8) mixing the components in a volume ratio to form a base solution, and adding 4-6 g of chromium trioxide per 100mL of the base solution to dissolve the chromium trioxide to prepare the chromium trioxide-containing aqueous solution; and the erosion time of the erosion process is 3-8 s.
Under which highly uniform nanowire arrays can be produced by erosion.
Preferably, in the step 2), the alkali liquor is an aqueous solution containing 1-2 mol/L alkali metal hydroxide, the hydrothermal temperature in the hydrothermal process is 150-250 ℃, and the hydrothermal time is 12-48 h; the acid solution is 0.1-1 mol/L hydrochloric acid, sulfuric acid, nitric acid, acetic acid or oxalic acid water solution, and the dipping time is 20-35 min.
Through alkali liquid hydrothermal treatment and acid liquid dipping treatment, the obtained titanium oxide nanowire array is better and uniform and has higher orderliness.
Preferably, the annealing process in step 2) has the following conditions: the annealing temperature is 400-600 ℃, the heating rate is 5-8 ℃/min, and the annealing time is 100-130 min.
The nanowire array can be completely prepared after annealing treatment. And is converted from the original anatase type or rutile type titanium dioxide into TiO2-B nanowire arrays.
Preferably, the gas used in the step 3) contains 3-5% VOL hydrogen fluoride gas, and the balance is nitrogen.
The hydrogen fluoride in the gas generates an etching effect, the controllability of the etching process is stronger due to the low-concentration hydrogen fluoride, and the nanowire array is prevented from being seriously damaged and even completely etched.
Preferably, the air pressure of the low-pressure impregnation process in the step 3) is 0.5-0.65 atm, and the impregnation time is 10-30 min.
The low-pressure impregnation can promote tetrabutyl titanate to be adsorbed in the nanowire array, and compared with normal-pressure impregnation, the mortgage impregnation efficiency is higher and the effect is better.
Preferably, the concentrated hydrochloric acid in the step 4) is 36-38 wt%.
The residual impurities in the previous step can be removed hydrothermally in concentrated hydrochloric acid to improve TiO2The purity of the-B is improved, the electrochemical performance of the cathode material is integrally improved, tetrabutyl titanate is promoted to be combined with the nanowire array, a villiform titanium oxide structure is further grown on the basis of the nanowire array, the specific surface area is increased, the insertion points of lithium ions are increased, and the lithium ions are more conveniently and stably inserted and removed.
Preferably, the hydrothermal temperature in the hydrothermal process in the step 4) is 220-280 ℃ and the hydrothermal time is 110-140 min.
The invention has the beneficial effects that:
1) the process for preparing the precursor by anodic oxidation is simple and does not need a template, and key parameters of the titanium oxide nanowire such as tube length, tube diameter and wall thickness can be effectively controlled by adjusting solution composition, voltage, time and the like;
2) formed TiO2The B nanowire is well combined with the titanium matrix, the nanowire is beneficial to keeping stability when lithium ions are inserted into and extracted from the nanowire, and the titanium matrix can improve TiO2(B) The conductive ability of (c);
3) the haynaud-like titanium oxide structure is further prepared on the basis of the titanium oxide nanowires by dipping and hydrothermal methods, so that the lithium ions are more conveniently and stably inserted and removed;
4) the electrode does not need conductive graphite and a binder during preparation, so that the side reaction in the charge and discharge process can be reduced, and the energy density and the power density of the whole battery can be improved.
Drawings
FIG. 1 is an SEM image of a titanium oxide nanopore array during fabrication according to the present invention;
FIG. 2 is an SEM image of a pre-matrix during the preparation process of the present invention;
FIG. 3 is an SEM image of the titanium oxide grass-like structure prepared by the present invention.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and the attached drawing figures. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only examples of a part of the present invention, and not all examples. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Examples 1 to 5
A method for preparing a nano structure on the surface of a titanium material in situ, which comprises the following steps:
1) firstly, carrying out pretreatment on a titanium sheet: grinding by abrasive paper, polishing by using a polishing solution to remove surface scratches, eroding by using an erosion solution to remove surface oxides and oil stains, finally cleaning and drying to prepare an electrolyte, taking ethylene glycol as a solvent, and taking the concentration of a hydrogen fluoride solvent as 0.5 wt% respectively, dissolving fluoride in a small amount of deionized water, uniformly stirring, adding the ethylene glycol, stirring for more than 1h to obtain the electrolyte, taking cleaned Ti as an anode and a graphite flake as a cathode, wherein the distance between the two electrodes is 2cm, the electrolytic direct current voltage is 40V, the electrolytic time is 60min, putting a Ti sheet obtained after electrolysis into the deionized water, performing ultrasonic cleaning to obtain a titanium oxide layer, removing an oxide layer generated by the first anodic oxidation of a titanium foil, and drying to obtain a titanium substrate; preparing an ethylene glycol solution with fluoride concentration of 0.1-1.0 wt%, electrolyzing by taking the pretreated titanium substrate as an anode and graphite as a cathode, and cleaning to obtain a titanium substrate with a titanium oxide layer;
2) preparing a bedroom liquid: mixing water and hydrogen fluoride in a ratio of 100: 8 to form a base solution, and adding chromium trioxide in a proportion of 6g per 100mL of the base solution to dissolve the chromium trioxide; corroding the titanium oxide layer on the surface of the titanium substrate for 5s by using a corrosion liquid soaking mode, then placing the titanium oxide layer in alkali liquor for hydrothermal treatment, soaking in acid liquor after hydrothermal treatment, and annealing to obtain a pre-matrix;
3) etching the surface of the pre-matrix by using a gas phase etching method, and then placing the pre-matrix in tetrabutyl titanate for low-pressure dipping to obtain a precursor;
4) and putting the precursor into concentrated hydrochloric acid for hydrothermal treatment, and obtaining the titanium material with the surface in-situ grown complex titanium oxide nanostructure after hydrothermal treatment.
Specific preparation parameters of examples 1 to 5 are shown in tables 1 and 2 below.
TABLE 1 specific preparation parameters (I)
TABLE 2 specific preparation parameters (II)
Wherein, the SEM image of the intermediate obtained by the erosion of the step 2) in the preparation process of the example 2 is shown in figure 1; the SEM image of the pre-matrix prepared in example 2 is shown in FIG. 2; the SEM image of the titanium oxide flock structure of the final product obtained in example 2 is shown in FIG. 3. As is apparent from fig. 1, 2 and 3, the specific surface area is continuously increased while ensuring high orientation and uniformity of the titanium oxide nanostructure during the preparation process.
And (3) detection:
the titanium materials prepared in examples 1 to 5 were examined. Mixing ethylene carbonate and ethylene carbonate in a volume ratio of 1: 1 to prepare a base solution, and dissolving lithium hexafluorophosphate in the base solution to prepare an electrolyte, wherein: the molar concentration of lithium hexafluorophosphate is 1 mol/L; and (3) assembling the prepared electrolyte, the titanium material prepared in the embodiment and the polyethylene diaphragm serving as materials into a CR2025 button battery in a glove box filled with argon gas to obtain the lithium ion battery. And carrying out cycle test on the prepared lithium ion battery. The cells were tested for capacity, coulombic efficiency and number of stable cycles at a current density of 500 mA/g.
The results are shown in Table 3 below.
TABLE 3 test results
As is apparent from Table 3 above, the titanium material with the complex titanium oxide nanostructure grown in situ on the surface thereof has excellent electrochemical properties after the nanostructure is prepared in situ on the surface of the titanium material.
Claims (10)
1. A method for preparing a nano structure on the surface of a titanium material in situ is characterized by comprising the following steps:
1) preparing fluorine-containing electrolyte, taking the pretreated titanium substrate as an anode and graphite as a cathode for electrolysis, and cleaning to obtain the titanium substrate with a titanium oxide layer;
2) corroding a titanium oxide layer on the surface of the titanium substrate in a corrosion liquid soaking mode, then placing the titanium substrate in alkali liquor for hydrothermal treatment, soaking in acid liquor after hydrothermal treatment, and annealing to obtain a pre-matrix;
the erosion liquid consists of water, 40-45 wt% of hydrogen fluoride and chromium trioxide;
3) etching the surface of the pre-matrix by using a gas phase etching method, and then placing the pre-matrix in tetrabutyl titanate for low-pressure dipping to obtain a precursor;
4) and putting the precursor into concentrated hydrochloric acid for hydrothermal treatment, and obtaining the titanium material with the surface in-situ grown complex titanium oxide nanostructure after hydrothermal treatment.
2. The method for preparing the nano structure on the surface of the titanium material in situ according to claim 1, wherein the fluorine-containing electrolyte in the step 1) is an ethylene glycol solution with a fluoride concentration of 0.1-1.0 wt%.
3. The method for preparing the nano structure on the surface of the titanium material in situ according to claim 1 or 2, wherein the direct current voltage in the electrolysis in the step 1) is 25-70V, the electrolysis time is 10-180 min, and the distance between the two electrodes is 1.5-2.5 cm.
4. The method for preparing the nano structure on the surface of the titanium material in situ according to claim 1, wherein the etching solution of the step 2) firstly mixes water and hydrogen fluoride in a ratio of 100: (7-8) mixing the components in a volume ratio to form a base solution, and adding 4-6 g of chromium trioxide per 100mL of the base solution to dissolve the chromium trioxide to prepare the chromium trioxide-containing aqueous solution; and the erosion time of the erosion process is 3-8 s.
5. The method for in-situ preparation of the nanostructure on the surface of the titanium material according to claim 1, wherein in the step 2), the alkali solution is an aqueous solution containing 1 to 2mol/L alkali metal hydroxide, the hydrothermal temperature is 150 to 250 ℃ and the hydrothermal time is 12 to 48 hours; the acid solution is 0.1-1 mol/L hydrochloric acid, sulfuric acid, nitric acid, acetic acid or oxalic acid water solution, and the dipping time is 20-35 min.
6. The method for preparing the nano structure on the surface of the titanium material in situ according to the claim 1 or 5, characterized in that the annealing process in the step 2) is carried out under the following conditions: the annealing temperature is 400-600 ℃, the heating rate is 5-8 ℃/min, and the annealing time is 100-130 min.
7. The method for in-situ preparation of the nanostructure on the surface of the titanium material according to claim 1, wherein the gas used in the step 3) of vapor etching contains 3-5% VOL hydrogen fluoride gas, and the balance is nitrogen.
8. The method for in-situ preparing the nano-structure on the surface of the titanium material as claimed in claim 1 or 7, wherein the pressure of the low-pressure impregnation process in step 3) is 0.5 to 0.65atm, and the impregnation time is 10 to 30 min.
9. The method for preparing the nano structure on the surface of the titanium material in situ according to claim 1, wherein the concentrated hydrochloric acid in the step 4) is 36-38 wt%.
10. The method for in-situ preparation of the nano-structure on the surface of the titanium material according to claim 1 or 9, wherein the hydrothermal temperature in the step 4) is 220-280 ℃ and the hydrothermal time is 110-140 min.
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